• Frequency Distribution of 14C Ages for Chronostratigraphic Reconstructions: Alaska Region Study Case

      Michczyńska, Danuta J.; Hajdas, Irka (Department of Geosciences, The University of Arizona, 2010-01-01)
      In this study, we test the possibility of using databases of radiocarbon ages to estimate boundaries of climatic chronozones. The Alaska region was chosen and compared with chronozones of 2 European countries: Poland and the Netherlands. The study included setting up a database of 14C ages published for climatic records from Alaska. Some 974 14C determinations on organic samples were selected and used to establish chronozones for the Late Glacial and the Holocene for the Alaska region. The selected data were calibrated and a summed probability density function (PDF) was calculated. The shape analysis of the constructed frequency distribution of 14C dates on calendar timescales together with the assumption about preferential sampling seems to be a useful tool for establishing calendar ages for boundaries of climatic periods, i.e. chronozones.
    • High Contribution of Recalcitrant Organic Matter to DOC in a Japanese Oligotrophic Lake Revealed by 14C Measurements

      Nara, Fumiko Watanabe; Imai, Akio; Uchida, Masao; Matsushige, Kazuo; Komatsu, Kazuhiro; Kawasaki, Nobuyuki; Shibata, Yasuyuki; Amano, Kunihiko; Mikami, Hajime; Hanaishi, Ryuji (Department of Geosciences, The University of Arizona, 2010-01-01)
      Carbon isotopes (14C and 13C) of dissolved organic carbon (DOC) in a Japanese oligotrophic lake (Lake Towada) were measured to study the origin and cycling of dissolved organic matter (DOM) in Lake Towada. Lake water samples were collected at 3 depths (0, 30, and 80 or 85 m) during 4 months (April, June, August, and October) in 2006. 14C measurements of DOC were performed by accelerator mass spectrometry (AMS) at the National Institute for Environmental Studies (NIES-TERRA) in Japan. ∆14C and delta-13C values of DOC in Lake Towada showed light carbon isotopic values ranging from -750 to -514v and -29.0 to -27.8‰, respectively. These values are similar to those of humic substances reported. The very low carbon isotopic values of DOC in Lake Towada suggest a very small contribution of DOC derived from fresh phytoplankton to the lake DOC. There is an extremely high linear relationship between the ∆14C and delta-13C of DOC in Lake Towada when all data points are plotted (r2 = 0.818, p < 0.01), suggesting that the DOC in Lake Towada has 2 specific sources contributing heavy and light carbon isotopes. Although the freshly produced DOC of phytoplankton origin can be decomposed easily, the variation in the autochthonous DOC should influence the carbon isotopic values of DOC in Lake Towada.
    • Hydropyrolysis: Implications for Radiocarbon Pretreatment and Characterization of Black Carbon

      Ascough, P. L.; Bird, M. I.; Meredith, W.; Wood, R. E.; Snape, C. E.; Brock, F.; Higham, T. F. G.; Large, D. J.; Apperley, D. C. (Department of Geosciences, The University of Arizona, 2010-01-01)
      Charcoal is the result of natural and anthropogenic burning events, when biomass is exposed to elevated temperatures under conditions of restricted oxygen. This process produces a range of materials, collectively known as pyrogenic carbon, the most inert fraction of which is known as black carbon (BC). BC degrades extremely slowly and is resistant to diagenetic alteration involving the addition of exogenous carbon, making it a useful target substance for radiocarbon dating particularly of more ancient samples, where contamination issues are critical. We present results of tests using a new method for the quantification and isolation of BC, known as hydropyrolysis (hypy). Results show controlled reductive removal of non-BC organic components in charcoal samples, including lignocellulosic and humic material. The process is reproducible and rapid, making hypy a promising new approach not only for isolation of purified BC for 14C measurement but also in quantification of different labile and resistant sample C fractions.
    • Is the Consensus Value of ANU Sucrose (IAEA C-6) Too High?

      Xu, Xiaomei; Khosh, Matthew S.; Druffel-Rodriguez, Kevin C.; Trumbore, Susan E.; Southon, John R. (Department of Geosciences, The University of Arizona, 2010-01-01)
      Primary and secondary standards are essential in radiocarbon analyses for the purpose of reporting and comparing data among laboratories, as well as for internal laboratory data quality control. ANU sucrose is one of the IAEA-certified 14C standards (C-6) with a consensus value of 1.5061 +/- 0.0011 fraction modern (Fm). All of our measurements of ANU sucrose (n = 351) as a secondary standard over the last 7 yr result in an average value of 1.5016 +/- 0.0005 Fm (2- standard error). After applying the same outlier tests used for IAEA reference standards, a weighted average value of 1.5016 +/- 0.0002 Fm (n = 294) was calculated. This value is significantly lower than the IAEA C-6 consensus value (t test with unequal variance; p = 0.023). In contrast, our measurements of other secondary standards over the same time period are in excellent agreement with their respective consensus values. Since ANU is the only secondary standard measured in our lab that does not agree with the consensus values, and we have measured a larger number analyses compared to what went into the definition of the consensus value, we suggest that the consensus value of ANU sucrose might be too high by ~0.0045 +/- 0.0011 Fm. Given that some labs routinely use ANU sucrose as a primary standard, our results suggest that revisiting the consensus value of ANU sucrose may be necessary.
    • Modern Radiocarbon Levels for Northwestern Mexico Derived from Tree Rings: A Comparison with Northern Hemisphere Zones 2 and 3 Curves

      Beramendi-Orosco, Laura E.; Gonzalez-Hernandez, Galia; Villanueva-Diaz, Jose; Santos-Arevalo, Francisco J.; Gómez-Martinez, Isabel; Cienfuegos-Alvarado, Edith; Morales-Puente, Pedro; Urrutia-Fucugauchi, Jamie (Department of Geosciences, The University of Arizona, 2010-01-01)
      The radiocarbon variation for northwestern Mexico during the period 1950-2004 was studied by accelerator mass spectrometry (AMS) and liquid scintillation counting (LSC) analyses of tree rings. Two tree-ring sequences of Pseudotsuga menziesii, sampled in a site isolated from urban centers and active volcanoes (26.18 degrees N, 106.3 degrees W, 3000 m asl), were dendrochronologically dated and separated in annual rings prior to 14C analysis. Results obtained show a similar profile to the values reported for the Northern Hemisphere (NH), having significant correlation coefficients with the compilation curves for NH zone 2 (r = 0.987, p < 0.001) and NH zone 3 (r = 0.993, p < 0.001). The maximum peak is centered at 1964.5 with a ∆14C value of 713.15 +/- 9.3‰. The values obtained for the period 1958-1965 are lower than zone 2 values and higher than zone 3 values. For the period 1975-2004, the values obtained are higher than the NH compilation curve and other NH records. We attribute the first divergence to the North American monsoon that may have carried 14C-depleted air from the south during the summer months; the second divergence may be attributable to 14C-enriched biospheric CO2.
    • New Radiocarbon Dates from the Late Neolithic Tell Settlement of Hódmezővásárhely-Gorzsa, SE Hungary

      Gulyás, Sandor; Sümegi, Pál; Molnár, Mihály (Department of Geosciences, The University of Arizona, 2010-01-01)
      Understanding the internal chronology of the Late Neolithic Tisza culture and the Neolithic of the Tisza region is the subject of debate in both Hungarian and international prehistoric research. The layer sequence of the Late Neolithic Gorzsa tell from SE Hungary offers ideal match points for determining the successive phases of the Tisza culture. According to the results published so far, in the Gorzsa sequence the Tisza culture was divided into 4 main phases with a fifth phase representing the transitional period to the Early Copper Age. Excavations were carried out in 33 profiles covering about 2% of the original area of the entire settlement. The archaeostratigraphy established was based on the identification of microhorizons corresponding to settlement levels. Radiocarbon dates published thus far were created using a pool of various objects of differing microhorizons deriving from different profiles. However, as archaeological results revealed, the settlement was characterized by frequent, minor spatial shifts during its evolution into a tell complex. Here, we present a succession of 7 14C dates deriving from a single profile located at the northeastern flank of the excavation area. The 7 dates span the entire profile from the uppermost microhorizons down to the lowermost ones. The new dates were compared with the existing relative chronology mentioned above. According to our findings, material was deposited in this part of the site mainly during the first 2 phases of evolution of the tell complex. The later phases are either less developed or missing due to possibly a spatial shift of the center of the tell complex resulting first in a deceleration and finally a complete cessation of artifact accumulation to the northwest flanks of the former natural levee. Thus, the previous hypothesis of spatial shifts based on relative chronologies within the site has been corroborated. Furthermore, the congruence between our new dates corrected for any reservoir effect and the previous dates of Hertelendi (1998) may refer to a correct determination of freshwater shell carbonate reservoir effect in the fluvial system of the Tisza River, which may be used in further studies in the area.
    • Optimization of the Graphitization Process at AGE-1

      Němec, Mojmir; Wacker, Lukas; Gäggeler, Heinz (Department of Geosciences, The University of Arizona, 2010-01-01)
      The reaction conditions for the graphitization of CO2 with hydrogen were optimized for a fast production of high-quality carbon samples for accelerator mass spectrometry (AMS) measurement. The iron catalyst in use is first oxidized by heating with air to remove possible carbon and other impurities and then after evacuation reduced back to iron with hydrogen in several flushing steps to remove any iron oxide. The optimum conditions for a fast graphitization reaction were experimentally determined by changing the reaction temperatures and the H2/CO2 ratio. The resulting graphite samples were measured by AMS to find the smallest isotopic changes (13C) at a minimum of molecular fragment formation (13CH current). The improvements are based on thermodynamic data and are explained with Baur-Glaessner diagrams.
    • Paleoearthquakes as Anchor Points in Bayesian Radiocarbon Deposition Models: A Case Study from the Dead Sea

      Kagan, Elisa J.; Stein, Mordechai; Agnon, Amotz; Ramsey, Christopher Bronk (Department of Geosciences, The University of Arizona, 2010-01-01)
      The Bayesian statistical method of the OxCal v 4.1 program is used to construct an age-depth model for a set of accelerator mass spectrometry (AMS) radiocarbon ages of organic debris collected from a late Holocene Dead Sea stratigraphic section (the Ein Feshkha Nature Reserve). The model is tested for a case where no prior earthquake information is applied and for a case where there is incorporation of known ages of 4 prominent historical earthquakes as chronological anchor points along the section. While the anchor-based model provided a tightly constrained age-depth regression, the "non-anchored" model still produces a correlation where most of the 68% or 95% age ranges of the 52 seismites can be correlated to historical earthquakes. This presents us with the opportunity for high-resolution paleoseismic analysis and comparison between various sites.
    • Pre-Bomb Marine Reservoir Ages in the Western Pacific

      Yoshida, Kunio; Hara, Tatsuaki; Kunikita, Dai; Miyazaki, Yumiko; Sasaki, Takenori; Yoneda, Minoru; Matsuzaki, Hiroyuki (Department of Geosciences, The University of Arizona, 2010-01-01)
      In this study, molluscan shells housed at the University Museum, the University of Tokyo, provided a new set of region-specific correction values (R) for the western Pacific, in particular for the central part of the main islands in the Japanese Archipelago and the southwest islands of Japan. The values of 40 total samples were calculated from 11 regions. North of the main islands and in the Ryukyu Islands, the mean R values showed comparatively small values, 5-40 14C yr; in the central part of the main islands, these values were 60-90 14C yr.
    • Pre-Bomb Marine Reservoir Variability in the Kimberley Region, Western Australia

      O'Connor, Sue; Ulm, Sean; Fallon, Stewart J.; Barham, Anthony; Loch, Ian (Department of Geosciences, The University of Arizona, 2010-01-01)
      New Delta-R values are presented for 10 known-age shells from the Kimberley region of northwest Australia. Previous estimates of Delta-R for the Kimberley region are based on only 6 individual shell specimens with dates of live collection known only to within 50 yr (Bowman 1985a). Here, we describe the results of our recent attempts to constrain Delta-R variability for this region by dating a suite of known-age pre-AD 1950 shell samples from the Australian Museum and Museum Victoria. A regional Delta-R of 58 +/- 17 14C yr for open waters between Broome and Cape Leveque is recommended based on 7 of these specimens. The criteria used to select shells for dating and inclusion in the regional mean are discussed.
    • Radiocarbon and Stable Carbon Isotope Ratio Data from a 4.7-m-long Sediment Core of Lake Baikal (Southern Siberia, Russia)

      Nara, Fumiko Watanabe; Watanabe, Takahiro; Nakamura, Toshio; Kakegawa, Takeshi; Katamura, Fumitaka; Shichi, Koji; Takahara, Hikaru; Imai, Akio; Kawai, Takayoshi (Department of Geosciences, The University of Arizona, 2010-01-01)
      A sediment core (VER99G12; core length, 4.66 m) was taken from the Buguldeika Saddle of Lake Baikal in 1999. Radiocarbon measurements of total organic carbon (TOC) and pollen concentrate fractions from the VER99G12 core were performed by a Tandetron accelerator mass spectrometry (AMS) system (Model-4130, HVEE) at Nagoya University. The AMS 14C ages showed that the VER99G12 core spans the past ~30 cal ka BP (from the MIS 3 to present), and the average sedimentation rate of this core was calculated to be 13.6 cm/kyr based on the calibrated ages. This means that the time resolution of VER99G12 sediment samples in this study is better than ~70-80 yr/cm. Stable carbon isotope ratios of TOC (13CTOC) in the VER99G12 core varied widely from about 26.6 to 31.3 during the last glacial/post-glacial transition period (about 17-12 cal ka BP). Therefore, a rapid change in the carbon sources in Lake Baikal occurred in the last glacial/post-glacial transition period is concluded.
    • Radiocarbon Dating of the Last Volcanic Eruptions of Ciomadul Volcano, Southeast Carpathians, Eastern-Central Europe

      Harangi, Sz; Molnár, M.; Vinkler, A. P.; Kiss, B.; Jull, A. J. T.; Leonard, A. G. (Department of Geosciences, The University of Arizona, 2010-01-01)
      This paper provides new accelerator mass spectrometry (AMS) radiocarbon age data for the last volcanic events in the Carpathian-Pannonian region of eastern-central Europe. The eruption ages were determined on charcoal fragments collected from pumiceous pyroclastic flow deposits at 2 localities of the Ciomadul Volcano. Two charcoal samples from the southeastern margin of the volcano (Bixad locality) set the date of the last volcanic eruption to 27,200 +/- 260 yr BP (29,500 +/- 260 cal BC). On the other hand, our data show that the Tusnad pyroclastic flow deposit, previously considered as representing the youngest volcanic rock of the region, erupted at ~39,000 yr BP (~41,300 cal BC). Thus, a period of dormancy more than 10,000 yr long might have elapsed between the 2 volcanic events. The different ages of the Tusnad and Bixad pyroclastic flow deposits are confirmed also by the geochemical data. The bulk pumices, groundmass glass, and the composition of the main mineral phases (plagioclase and amphibole) suggest eruption of slightly different magmas. Considering also the assumed long volcanic history (~600 ka) of the Ciomadul, these data suggest that further detailed studies are necessary on this seemingly inactive volcano in order to evaluate the possible renewal of volcanic activity in the future.
    • Report on the 20th International Radiocarbon Conference Graphitization Workshop

      Turnbull, Jocelyn; Prior, Christine (Department of Geosciences, The University of Arizona, 2010-01-01)
      A sample preparation workshop was convened at the 20th International Radiocarbon conference, with about 30-40 attendees. The term "sample preparation" was not further specified to allow participants to address the laboratory issues most important to them. Given the short time available, the focus quickly narrowed to details of graphite preparation for accelerator mass spectrometry (AMS), with particular interest in procedures for small samples, and hence we have changed the title to reflect the focus. Here, we summarize the workshop discussion, adding additional background information and references to publications. Several aspects of graphite preparation are included: catalyst types and ratio of catalyst to carbon; optimal reaction temperatures for various sample sizes; methods for water removal; types of pressure transducers; preconditioning of catalyst; and problems with blank values in very small samples. The pros and cons of sample dilution were also discussed.
    • Robust Bayesian Analysis, an Attempt to Improve Bayesian Sequencing

      Weninger, Franz; Steier, Peter; Kutschera, Walter; Wild, Eva Maria (Department of Geosciences, The University of Arizona, 2010-01-01)
      Bayesian sequencing of radiocarbon dates deals with the problem that in most cases there does not exist an unambiguous way to define the so-called prior function, which represents information in addition to the result of the 14C measurements alone. However, a random choice of a particular prior function can lead to biased results. In this paper, "robust Bayesian analysis," which uses a whole set of prior functions, is introduced as a more reliable method. The most important aspects of the mathematical foundation and of the practical realization of the method are described. As a general result, robust Bayesian analysis leads to higher accuracy, but paid for with reduced precision. Our investigations indicate that it seems possible to establish robust analysis for practical applications.
    • Scandinavian Models: Radiocarbon Dates and the Origin and Spreading of Passage Graves in Sweden and Denmark

      Paulsson, Bettina Schulz (Department of Geosciences, The University of Arizona, 2010-01-01)
      Approximately 2700 radiocarbon results are currently available from European megalithic contexts. The interpretation of these 14C dates is often difficult. It is not easy to connect many of them from their archaeological context to the construction or the burial phase of the graves. This paper focuses on the megaliths of Scandinavia--a special megalith region--as it is the only place in Europe with 14C dates directly referable to the construction of the passage graves, the graves have good bone preservation, and new dating sequences are available. Some 188 14C results are now available from Scandinavian passage graves. In Sweden, new data suggest that these graves were built from the first half of the 35th century BC onwards. The 14C dates from birch bark as filling material between dry walls make it possible to build a sequence for the construction phase of the passage graves in Denmark from the 33rd century BC onward. With an interpretative Bayesian statistical framework, it is possible to untangle the nuances of the differences for the origin and the spreading of the megaliths in the different regions, to define, together with the archaeological remains, possible cultural-historical processes behind these phenomena and to discuss diffusion versus convergence.
    • Simple Pretreatment Method Development for Iron and Calcium Carbonate Samples

      Park, Junghun; Hong, Wan; Choi, Han Woo; Kim, Joonkon; Kim, Gi Dong (Department of Geosciences, The University of Arizona, 2010-01-01)
      Since iron artifacts generally contain trace amounts of carbon, an iron sample needs to be relatively large, as compared to other materials, and a specially designed combustion system is required. An elemental analyzer (EA) was used for the combustion of iron without any special chemical treatment. CO2 gas with 1 mg of carbon was obtained from the combustion of an iron artifact by using an EA and reduced to graphite for accelerator mass spectrometry (AMS) measurement. In this work, AMS dating results done at the Korea Institute of Geoscience and Mineral Resources (KIGAM) for several ancient iron artifacts are presented and compared with independently estimated ages. This method was found to be useful for the pretreatment of iron artifacts that contained 0.1% carbon. A simple pretreatment method using an EA was also applied to calcium carbonate (CaCO3) samples. Samples were preheated overnight at 100-300 C, without any special chemical treatment. This removed modern CO2 contamination and the background level decreased to a comparable value measured in samples treated with phosphoric acid under vacuum.
    • Spatial Distribution of ∆14C Values of Organic Matter in Surface Sediments off Saru River in Northern Japan, One Year after a Flood Event in 2006

      Nagao, Seiya; Irino, Tomohisa; Aramaki, Takafumi; Ikehara, Ken; Katayama, Hajime; Otosaka, Shigeyoshi; Uchida, Masao; Shibata, Yasuyuki (Department of Geosciences, The University of Arizona, 2010-01-01)
      Dispersion and deposition of terrestrial organic matter by flooding on the inner shelf were studied using C/N ratios, 13C, and ∆14C values of sedimentary organic matter. Surface sediment samples (top 2 cm) were collected from coastal areas near the Saru River in southwestern Hokkaido, northern Japan, 1 yr after a flood event in 2006. Riverine suspended solids were also collected at a fixed station downstream during 2006-2008. Sandy sediments were located at the front of the river mouth and the western part of the sampling area, with the 13C of organic matter ranging from -23.8 to -22.0, ∆14C of -655 to -388, and an organic carbon/total nitrogen (C/N) ratio of 5.9-7.7. On the other hand, silt and clay sediments were distributed in a restricted area 11-16 km from the river mouth, with lighter 13C (-26.7 to -24.1) and higher ∆14C (-240 to -77) of organic matter and C/N ratio (7.8-13.3). From end-member analysis, the apparently younger and less degraded organic matter in the silt and clay sediments consists mainly of terrestrial organic matter released by flood events. They remain in the depression, although most flood deposits were moved to deep-sea environments.
    • Spatial Radiocarbon and Stable Carbon Isotope Variability of Mineral and Thermal Waters in Slovakia

      Povinec, P. P.; Franko, O.; Šivo, A.; Richtáriková, M.; Breier, R.; Aggarwal, P. K.; Araguás-Araguás, L. (Department of Geosciences, The University of Arizona, 2010-01-01)
      Isotope hydrology investigations were carried out with the aim to study isotope variability in mineral and thermal waters (MTW) of Slovakia. The aquifers of MTW were formed by Triassic limestones and dolomites, which are found in the mountains as well as in the pre-Tertiary substratum of depressions and lowlands. The MTW were of artesian and/or open structures. At present, there are only boreholes available, as natural outflows have already been captured by them. Large spatial isotope variability (14C between 2 and 33.6 pMC, 18O between -11.8 and -9.8, and 13C between -12.7 and -3.4 for bicarbonates and -21 and -4.9 for free CO2) and heterogeneity of MTW was observed, indicating different origins of MTW. Corrected radiocarbon apparent ages of MTW indicate that they mostly infiltrated during the Würm and Holocene periods.
    • Spatial Variation in the Marine Radiocarbon Reservoir Effect throughout the Scottish Post-Roman to Late Medieval Period: North Sea Values (500-1350 BP)

      Russell, N.; Cook, G. T.; Ascough, P. L.; Dugmore, A. J. (Department of Geosciences, The University of Arizona, 2010-01-01)
      The marine radiocarbon reservoir effect (MRE) occurs as a spatially and temporally dependent variable owing to localized changes in oceanic water composition. This study investigates Delta-R values (deviations from the global average MRE whose Delta-R = 0) during the period 500-1350 BP for the east coast of Scotland, where a complex estuarine system exists that drains into the semi-enclosed North Sea basin. Due to the availability of suitable archaeological samples, the data set has a distinct Medieval focus that spans the area from Aberdeen in the north to East Lothian in the south. Many of the Delta-R values are not significantly different from 0 (the global average), but there are occasional excursions to negative values (max -172 +/- 20) indicating the presence of younger water. These values show greater variability compared to other published data for this general region, suggesting that considerable care must be taken when dating marine derived samples from archaeological sites on the east coast of Scotland.
    • Studies on the Preparation of Small 14C Samples with an RGA and 13C-Enriched Material

      Liebl, Jakob; Avalos Ortiz, Roswitha; Golser, Robin; Handle, Florian; Kutschera, Walter; Steier, Peter; Wild, Eva Maria (Department of Geosciences, The University of Arizona, 2010-01-01)
      The minimum size of radiocarbon samples for which reliable results can be obtained in an accelerator mass spectrometry (AMS) measurement is in many cases limited by carbon contamination introduced during sample preparation (i.e. all physical and chemical steps to which samples were subjected, starting from sampling). Efforts to reduce the sample size limit down to a few mu-g carbon require comprehensive systematic investigations to assess the amount of contamination and the process yields. We are introducing additional methods to speed up this process and to obtain more reliable results. A residual gas analyzer (RGA) is used to study combustion and graphitization reactions. We could optimize the reaction process at small CO2 pressures and identify detrimental side reactions. Knowing the composition of the residual gas in a graphitization process allows a reliable judgment on the completeness of the reaction. Further, we use isotopically enriched 13C (greater than or equal to 98% 13C) as a test material to determine contamination levels. This offers significant advantages: 1) The measurement of 12C/13C in CO2 is possible on-line with the RGA, which significantly reduces turnaround times compared to AMS measurements; 2) Both the reaction yield and the amount of contamination can be determined from a single test sample. The first applications of isotopically enriched 13C and the RGA have revealed that our prototype setup has room for improvements via better hardware; however, significant improvements of our sample processing procedures were achieved, eventually arriving at an overall contamination level of 0.12 to 0.15 mu-g C during sample preparation (i.e. freeze-drying, combustion, and graphitization) of mu-g-sized samples in aqueous solution, with above 50% yield.